Method of manufacturing a semiconductor device

Abstract

A method of manufacturing a semiconductor device includes forming a dopant layer including a dopant composition over a substrate. A resist layer including a resist composition is formed over the dopant layer. A dopant is diffused from the dopant composition in the dopant layer into the resist layer; and a pattern is formed in the resist layer.

What is claimed is: 
     
         1 . A method of manufacturing a semiconductor device, comprising:
 forming a dopant layer comprising a dopant composition over a substrate, the dopant composition comprising a photobase generator (PBG);   forming a resist composition including a reaction product of an organometallic precursor and an amine, a borane, a phosphine, or water, the organometallic precursor has a formula M a R b X c , where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group; X is selected from the group consisting of an amino group, an alkoxy group, a carboxylate group, a halogen, and a sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5;   forming a resist layer comprising the resist composition over the dopant layer;   diffusing a dopant from the dopant composition in the dopant layer into the resist layer by heating the dopant layer and the resist layer to a temperature ranging from 40° C. to 250° C.;   selectively exposing the resist layer to actinic radiation; and   developing the selectively exposed resist layer to form a pattern in the resist layer.   
     
     
         2 . The method according to  claim 1 , wherein the PBG is a quaternary ammonium dithiocarbamate, an α aminoketone, an oxime-urethane containing molecule, an ammonium tetraorganylborate salt, and a N-(2-nitrobenzyloxycarbonyl)cyclic amine. 
     
     
         3 . The method according to  claim 1 , wherein forming the dopant layer comprises applying a dopant composition comprising a dopant and a solvent over the substrate. 
     
     
         4 . The method according to  claim 1 , wherein after diffusing the dopant into the resist layer, a concentration of the PBG in the resist layer is in a range of 0.1 wt. % to 20 wt. %, based on a weight of the PBG and the resist composition. 
     
     
         5 . The method according to  claim 1 , wherein the forming a resist layer comprises a chemical vapor deposition, physical vapor deposition, or atomic layer deposition operation. 
     
     
         6 . The method according to  claim 1 , wherein the dopant composition comprises one or more of an inorganic acid, an inorganic base, a crosslinker, or a surfactant. 
     
     
         7 . The method according to  claim 1 , further comprising heating the dopant layer at a temperature ranging from 80° C. to 250° C. before forming the resist layer. 
     
     
         8 . The method according to  claim 1 , wherein the organometallic precursor includes at least one of Sn, Bi, Sb, In, and Te. 
     
     
         9 . A method of manufacturing a semiconductor device, comprising:
 forming a metallic photoresist composition including a reaction product of an organometallic precursor and an amine, a borane, a phosphine, or water, the organometallic precursor has a formula M a R b X c , where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group; X is selected from the group consisting of an amino group, an alkoxy group, a carboxylate group, a halogen, and a sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5;   forming a metallic photoresist layer comprising the metallic photoresist composition over a substrate;   forming a dopant layer comprising a dopant composition over the metallic photoresist layer, the dopant composition comprises a non-ionic surfactant and at least one of an organic acid, an inorganic acid, an inorganic base, a crosslinker, or a chelate;   diffusing a dopant from the dopant layer into the metallic photoresist layer; and   forming a pattern in the metallic photoresist layer.   
     
     
         10 . The method according to  claim 9 , wherein the dopant composition comprises a non-ionic surfactant having a structure of A-X or A-X-A-X, where A is an aliphatic or aromatic, unbranched or branched, cyclic or non-cyclic C2-C100 carbon group, and X is an alkyl group. 
     
     
         11 . The method according to  claim 10 , wherein the alkyl group is substituted with one or more polar functional groups selected from the group consisting of —OH, ═O, —C(═O)SH, —C(═O)OH, —C(═O)NH, —SO 2 OH, —SO 2 SH, —SOH; or includes one or more linking groups selected from the group consisting of —SO 2 —, —CO—, —CN—, —SO—, —CON—, —NH—, —SO 3 NH—, SO 2 NH—, —S—, —P—, —P(O 2 )—, —C(═O)OR—, —O—, and —N—. 
     
     
         12 . The method according to  claim 9 , wherein the diffusing a dopant comprises heating the dopant layer and the metallic photoresist layer at a temperature ranging from 40° C. to 250° C. 
     
     
         13 . The method according to  claim 9 , wherein the dopant layer is formed in a vacuum chamber at a pressure less than atmospheric pressure. 
     
     
         14 . The method according to  claim 9 , wherein the dopant composition comprises one or more of an inorganic acid, an inorganic base, a crosslinker, or a surfactant. 
     
     
         15 . The method according to  claim 9 , further comprising heating the dopant layer at a temperature ranging from 80° C. to 250° C. 
     
     
         16 . The method according to  claim 9 , wherein the metallic photoresist composition comprises an organometallic compound. 
     
     
         17 . A method of manufacturing a semiconductor device, comprising:
 forming a dopant layer comprising a dopant composition over a substrate,   wherein the dopant composition comprises an ethylene oxide (EO)-propylene oxide (PO) type surfactant and at least one of a photoacid generator, an organic acid, an inorganic acid, an inorganic base, or a crosslinker;   forming a photoresist layer by a vapor phase deposition technique over the substrate, the vapor phase deposition technique includes reacting an organometallic precursor and an amine, a borane, a phosphine, or water, and the organometallic precursor has a formula: M a R b X c , where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group; X is selected from the group consisting of an amino group, an alkoxy group, a carboxylate group, a halogen, and a sulfonate group; and 1≤a≤2, b≥1, c≥1, and b+c≤5;   transferring a dopant from the dopant layer into the photoresist layer;   selectively exposing the photoresist layer to actinic radiation to form a latent pattern in the photoresist layer; and   developing the selectively exposed photoresist layer to form a pattern in the photoresist layer.   
     
     
         18 . The method according to  claim 17 , wherein the surfactant has a structure 
       
         
           
           
               
               
           
         
       
       where each R is a C1-C20 hydrocarbon group. 
     
     
         19 . The method according to  claim 18 , wherein the C1-C20 hydrocarbon group is an aryl, alkyl, or alkenyl group. 
     
     
         20 . The method according to  claim 19 , wherein n is in a range of 1 to 6.